Process for treating oils with sul



Search 90m PROCESS FOR TREATING OILS WITH SUL- PHURIC ACID AND FOR PREPARING IM- PROVED WETTING AGENTS AND DETER- GENTS Stewart 0. Fulton and Hans G. Vesterdal, Elizabeth, N. J., assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application November 9, 1934,

Serial No. 752,312 I 21 Claims. (01. 260-9912) 5 treatment of drating}.qilasqeieiein 212a 5 fwitfifiiniirigflsulfihliriciiacid i012. he preparati The ratio of acid to oil is preferably about 1.1 of improved sulphuric derivatives which are useto 1.5 mols of sulphuric acid (not including any .ful as wetting agent s and detergents. sulphuric anhydride present in fuming acid) per "'Ifi' the tfatfnent of olefins and unsaturated mol. of olefin or other readily reactive organic hydrocarbon oils such as acid-reactive crude oils compound in the stocks treated. In treating 10 and fractions thereof and cracked oils containing stocks of known or readily determinable olefin olefins, with strong or fuming sulphuric acid, concontent, such as pure olefins, mixtures thereof, siderable difficulties are usually experienced by and cracked paraffin wax fractions, the required the formation of unstable sulphuric derivatives, amount of acid can readily be determined by a 35 which are at least partly oil-soluble with resultsimple calculation. In treating more complex ing impairment in the quality of both the oil and stocks, such as fractions of oils cracked at high the sulphuric derivatives obtained. These distemperatures and pressures, the amount of acid advantages are particularly noted when using required for complete reaction is most conven fuming sulphuric acid as the treating agent. For iently determined by a preliminary small scale 00 example, these unstable products readily develop test, and a quantity of acid slightly in excess of 90 acidity on contact with water and may render the indicated required amount is then used. the crude sulphuric derivatives obtained unsatis- The reaction temperature and the total time factory for use as detergents for washing acidof contact of the reaction mixture with sulphuric sensitive textiles and in other uses where even acid of more than about 60% strength are pref- 05 slight amounts of strong mineral acids are oberably so limited and interadjusted that no sub- 95 jectionable. stantial oxidation or polymerization, with forma- It is an object of this invention to provide an tion of color bodies, occurs. The acid strength improved process by which the above disadvanmay be reduced by dilution with water and/or tages are largely and in many instances even by neutralization, preferably with bases capable substantially completely avoided and by which of forming water soluble salts of the organo-sul- 30 improved products suchas refinedoil-andsulphuric phuric derivatives, such as the alkalies and amderivatives of high quality may be directly obmonia. tained without the necessity of subsequent refin- It is offered in explanation that the unstable ing operations to remove undesirable by-products components are of the nature of di-alkyl sulof the acid treating process. These and further phates, resulting from the reaction of two mole- 35 objects will be ascertained from the following decules of olefins with one molecule of sulphuric scription of the invention and the claims. acid, and that the use of an excess of sulphuric It has now been discovered that if the amount acid prevents this and res Its only in the formaof sulphuric acid is maintained constantly in tion of mono-alkyl sulp ates, which are much 40 excess of that required for equi-molal reaction more stable. 40 W the Organic COmDOIIEHBS p S ch a While this invention may be applied generally olefins, which are reactive under the conditions in the refining of oils and in the treatment of used, the formation of unstable products is subany acid-reactive organic materials, particularly stantially completely avoided. These conditions those containing olefinic linkages, it is of especial of operation may be secured in any suitable value in the preparation of improved wetting 45 manner. The oil, containing reactive compoagents and detergents from olefins containing nents, may be added to a bath of a strong sulabout 8 to 22 or more carbon atoms, and to mixphuric reagent, such as fuming sulphuric acid, tures of such olefins and oils containing the same, maintained preferably at a low temperature at such as cracked hydrocarbon oils and waxes.

Which side reactions such as oxidation and poly- The preferred olefins for the preparation of de- 5 merization are inappreciable, as long as sulphuric tergents of high quality are those of 10 or more acid remains in excess. The process is preferably carbon atoms arranged in a straight chain with conducted in a continuous manner, in which a the olefinic linkage at or near the end of the stream of the oil is brought continuously into chain. Such olefins are obtained by cracking high contact, with vigorous agitation, with a stream molecular weight paraflinfsuch as paraffin wax 55 and for the preparation of ir nproved products therefrom and relates more particularly to the of fuming sulphuric acid containing an excess of sulphuric acid. This excess is determined by the molal ratio of reactive organic molecules, such as olefins, to sulphuric acid, not including the sulphuric anhydride present.

COMPOSITIONS,

temperatures, of sulphuric derivatives suitable for use as wetting agents and detergents, of cracked petroleum oils is described and claimed m broadly in copending application Serial No.

752,286 filed November 9, 1934, by Per K. Frolich, and the use of cracked parafins is claimed specifically in copending application Serial No. 704,749, filed December 30, 1933, by William J. Sweeney. Wetting agents may also be prepared in the refining of petroleum crudes and uncracked fractions thereof at low temperatures as described in copending application Serial No. 752,313 filed November 9, 1934, by Raphael Rosen. The present invention is of value as an improved method of operating the acid-oil contacting steps of all such processes.

The use of the present invention in the preparation of detergents from cracked wax is illusy, trated in the following examples:

Example 1 10 volumes of a distillate fraction boiling from 100 to 600 F. and obtained by the destructive distillation of paraflin wax at atmospheric pres- 40 was proportioned to the volume of the mixer so that the total time of reaction, from time of initial contact to neutralization, was about 75 seconds. Isopropyl alcohol of about 95% concentration was then added to the reaction mix- 45 ture in suiflcient amount to cause the formation,

on standing, of three layers; namely, a lower aqueous layer of inorganic salts, a middle alcoholic layer containing in solution the salts of the formed sulphuric derivatives of the olefines, con- 50 sidered for convenience as soaps because of their detergent properties, and an upper layer of unreacted oil. The middle alcoholic layer was separately withdrawn, the alcohol removed by fractional distillation and the water by any suitable 55 evaporation or drying method, such as the use of a spray or a drum drier, to obtain a light colored (almost white) dry sodium soap. This soap was obtained in a yield of 35% by weight, based on the oil treated. It is an excellent detergent 60 and wetting agent in both hard and soft Water and in sea water, and is stable, as indicated by no development of acidity on boiling a 5% aqueous solution for four hours.

Example 2 The same amounts of reagents were used as in the. above example, except that the mixing operation was conducted as a batch process with addition of the fuming acid to a batch of the 70 oil with vigorous stirring and cooling to maintain the same reaction temperature. After neutralization as before there was separated in the same manner an alcoholic solution of light color containing the same yield of soap. This soap,

75 however, was unstable, developed acidity rapidly Orcss Reference and darkened with loss of yield on drying at ordinary drying temperatures, and the dry soap, even after neutralization, developed further acidity on standing in a hot aqueous solution under the same conditions used in the test for stability of the product of Example 1. This soap is also unstable in such test even if dried under vacuum at low temperature in order to prevent dissociation on drying.

Similarly, when only 0.65 volume of fuming acid Was used in the process of Example 1, the resulting product was unstable, and was obtained in a smaller yield of only about 25%.

The mixing operation shown in Example 1 may also be conducted at substantially higher temperatures, say 70 to 100 F., without impairment in the quality of the finished soaps, especially if the time of contact is decreased to about 30 seconds or less. This is due to the short time of reaction used, which is claimed broadly in i2 copending application. Serial No. 752,284 filed November 9, 1934, by Edwin J. Gohr. If longer times of contact such as thirty minutes or more, as are ordinarily used in acid treating of oils, are used, it is necessary to maintain the reaction temperature below about 40 F. to obtain high quality detergents from cracked paraffin wax, and even lower temperatures should be used in treating cracked petrolatum and cracked or crude oils and fractions thereof. Temperatures of to F. are preferred for such operation.

The strength of acid may be adjusted as desired and is preferably selected so as to obtain an acid which is liquid at the treating temperature used; for example, about 10 to sulphuric anhydride. While fuming acids up to about 65% content of sulphuric anhydride may be used it is generally unnecessary to use the stronger acids because of the desirability of maintaining at all times in the acid treating reaction an excess of sulphuric acid H2SO4) above an equal molecular proportion of acid to olefin.

This invention is not to be limited to any specific description or examples which have been presented herein solely for purposes of illustration but is to be limited only by the following claims in which it is desired to claim all novelty insofar as the prior art permits.

We claim:

1. Process for the production of sulphuric derivatives of olefines comprising mixing fuming sulphuric acid in excess with liquid olefines at a reaction temperature, continuously maintaining in the reaction zone more than one mol. of suiphuric acid, exclusive of the sulphuric anhydridc present, per mol. of olefin.

2. Process for the production of sulphuric acid derivatives of olefines comprising bringing a stream of liquid olefines into contact, with vigor ous agitation, with a stream of fuming sulphuric acid in excess at a reaction temperature, continuously maintaining in the reaction zone more than one mol. of sulphuric acid, exclusive of the sulphuric anhydride present, per mol. of olefin.

3. Process according to claim 2 in which said reaction temperature is below about 100 F.

4. Process for the acid treatment of hydrocarbon oils containing olefines comprising bringing a stream of said oil continuously into contact, with vigorous agitation, with a stream of fuming sulphuric acid in excess, at a reaction temperature, continuously maintaining in the reaction zone more than one mol. of sulphuric acid, exclusive of the sulphuric anhydride pres" Search liecm' ent, per mol. of olefin and separating sulphuric derivates of olefines from the reaction mixture.

5. Process according to claim 4 in which said oil is a petroleum oil.

6. Process according to claim 4 in which said oil is a cracked petroleum oil.

7. Process according to claim 4 in which said oil is a cracked parafiinic mixture of the class consisting of paraifin wax and petrolatum.

8. Process for the production of improved sulphuric acid derivates of olefines comprising bringing a stream of olefines of more than about 8 carbon atoms continuously into contact, with vigorous agitation, with a stream of fuming sulphuric acid in excess at a reaction temperature, continuously maintaining in the reaction zone more than one mol. of sulphiu'ic acid, exclusive of the sulphuric anhydride present, per mol. of olefin, immediately and continuously reducing the concentration of free sulphuric acid in the reaction mixture to below about 60% strength.

9. Process for preparing improved wetting agents and detergents comprising bringing a stream of cracked paraifin of the class of paraffin wax and petrolatum, containing olefines of above 8 carbon atoms continuously into contact with vigorous agitation, with a stream of fuming sulphuric acid in excess at a reaction temperature and for a time insufiicient to permit formation of substantial amounts of color bodies and polymerization products, continuously maintaining in the reaction zone more than one mol. of sulphuric acid, exclusive of the sulphuric anhydride present, per mol. of olefin, immediately and continuously reducing the concentration of free sulphuric acid in the reaction mixture to below about 60% strength, separating the resulting sulphuric derivatives of olefines from hydrocarbons and neutralizing said derivatives with a suitable alkali to form a salt of said derivatives.

10. Process according to claim 9 in which said cracked paraffins are prepared by cracking said parafiins in liquid phase.

11. Process according to claim 9 in which said cracked paraflins are prepared by cracking said paraflins by destructive distillation at a pressure below about 100 pounds per square inch.

12. Process according to claim 9 in which said acid strength is reduced by neutralization of said reaction mixture with an aqueous alkali.

13. Process according to claim 9 in which said acid strength is reduced by dilution with water.

14. Improved organo-sulphuric derivatives, prepared according to claim 1.

15. Process according to claim 8 in which said olefines comprise a mixture of olefines obtained by cracking a parafiine of the class consisting of parafine wax and petrolatum.

16. Process according to claim 8 in which said olefines comprise a mixture of olefines obtained by cracking a parafrine of the class consisting of parafiine wax and petrolatum in liquid phase.

1'7. Process according to claim 8 in which said olefines comprise a mixture of olefines obtained by cracking a paraifine of the class consisting of paraffine wax and petrolatum by destructive distillation at a pressure below about 100 lbs. per square inch.

18. Process for preparing improved wetting agents and detergents, comprising mixing fumin g sulphuric acid in excess with liquid olefins of more thaif'fcarb'ofiatoms per mol. with more than 1 mol. of sulphuric acid, exclusive of the sulphuric anhydride present, per mol. of olefin, and neutralizing the resulting sulphuric acid derivatives with a suitable alkali to form a salt thereof.

19. Process according to claim 18 in which the proportion of fuming acid to olefin continuously maintained in the reaction zone is from 1.1 to 1.5 mols of sulphuric acid, exclusive of the sulphuric anhydride present, per mol. of olefin.

20. Process according to claim 18, in which the said fuming sulphuric acid contains from 10 to 25% of sulphuric anhydride.

21. Improved wetting agents and detergents STEWART C. FULTON. HANS G. VESTERDAL. 

